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空气中合成固溶体荧光粉Ba_2(Zn,Mg)Si_2O_7∶Eu~(2+),Eu~(3+),Ce~(3+)及其发光特性
引用本文:邓升智,刘晨,杨楚珺,邱忠贤,周文理,张吉林,余丽萍,廉世勋. 空气中合成固溶体荧光粉Ba_2(Zn,Mg)Si_2O_7∶Eu~(2+),Eu~(3+),Ce~(3+)及其发光特性[J]. 无机化学学报, 2015, 31(2): 229-236
作者姓名:邓升智  刘晨  杨楚珺  邱忠贤  周文理  张吉林  余丽萍  廉世勋
作者单位:湖南师范大学化学化工学院,化学生物学及中药分析教育部重点实验室,资源精细化与先进材料湖南省高校重点实验室,长沙410081
基金项目:湖南省高校科技创新团队计划(湘教通[2012]318号),湖南省自然科学基金(No.2015JJ2100)和国家大学生创新性实验计划资助项目.
摘    要:采用高温固相法在空气中合成了Ba1.97-yZn1-xMgxSi2O7∶0.03Eu,y Ce3+系列荧光粉。分别采用X-射线衍射和荧光光谱对所合成荧光粉的物相和发光性质进行了表征。在紫外光330~360 nm激发下,固溶体荧光粉Ba1.97-yZn1-xMgxSi2O7∶0.03Eu的发射光谱在350~725 nm范围内呈现多谱峰发射,360和500 nm处有强的宽带发射属于Eu2+离子的4f 65d1-4f 7跃迁,590~725 nm红光区窄带谱源于Eu3+的5D0-7FJ(J=1,2,3,4)跃迁,这表明,在空气气氛中,部分Eu3+在Ba1.97-yZn1-xMgxSi2O7基质中被还原成了Eu2+;当x=0.1时,荧光粉Ba1.97Zn0.9Mg0.1Si2O7∶0.03Eu的绿色发光最强,表明Eu3+被还原成Eu2+离子的程度最大。当共掺入Ce3+离子后,形成Ba1.97-yZn0.9Mg0.1Si2O7∶0.03Eu,y Ce3+荧光粉体系,其发光随着Ce3+离子浓度的增大由蓝绿区经白光区到达橙红区;发现名义组成为Ba1.96Zn0.9Mg0.1Si2O7∶0.03Eu,0.01Ce3+的荧光粉的色坐标为(0.323,0.311),接近理想白光,是一种有潜在应用价值的白光荧光粉。讨论了稀土离子在Ba2Zn0.9Mg0.1Si2O7基质中的能量传递与发光机理。

关 键 词:Ba1.97Zn1-xMgxSi2O7  Ba1.97-yZn0.9Mg0.1Si2O7∶0.03Eu,yCe3+  自还原  白光荧光粉
收稿时间:2014-05-18
修稿时间:2014-09-10

Solid-Solution Phosphor Ba2(Zn,Mg)Si2O7:Eu2+,Eu3+,Ce3+ Prepared in Air and Its Luminescent Properties
DENG Sheng-Zhi,LIU Chen,YANG Chu-Jun,QIU Zhong-Xian,ZHOU Wen-Li,ZHANG Ji-Lin,YU Li-Ping and LIAN Shi-Xun. Solid-Solution Phosphor Ba2(Zn,Mg)Si2O7:Eu2+,Eu3+,Ce3+ Prepared in Air and Its Luminescent Properties[J]. Chinese Journal of Inorganic Chemistry, 2015, 31(2): 229-236
Authors:DENG Sheng-Zhi  LIU Chen  YANG Chu-Jun  QIU Zhong-Xian  ZHOU Wen-Li  ZHANG Ji-Lin  YU Li-Ping  LIAN Shi-Xun
Affiliation:Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education); Key Laboratory of Resource Fine-Processing and Advanced Materials, Universities of Hunan Province; College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China;Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education); Key Laboratory of Resource Fine-Processing and Advanced Materials, Universities of Hunan Province; College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China;Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education); Key Laboratory of Resource Fine-Processing and Advanced Materials, Universities of Hunan Province; College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China;Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education); Key Laboratory of Resource Fine-Processing and Advanced Materials, Universities of Hunan Province; College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China;Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education); Key Laboratory of Resource Fine-Processing and Advanced Materials, Universities of Hunan Province; College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China;Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education); Key Laboratory of Resource Fine-Processing and Advanced Materials, Universities of Hunan Province; College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China;Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education); Key Laboratory of Resource Fine-Processing and Advanced Materials, Universities of Hunan Province; College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China;Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education); Key Laboratory of Resource Fine-Processing and Advanced Materials, Universities of Hunan Province; College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China
Abstract:Ba1.97Zn1-xMgxSi2O7:0.03Eu and Ba1.97-yZn0.9Mg0.1Si2O7:0.03Eu,yCe3+ phosphors were synthesized in air condition by a high temperature solid-state reaction. Crystallization and optical properties were investigated by using powder X-ray diffraction and fluorescence spectrophotometer, respectively. Under the excitation of ultraviolet (330~360 nm), the emission spectra of these solid-solution phosphors exhibit multi-emission bands peaked at about 360 nm(blue-purple color), 500 nm (green color) and 590~725 nm (red color), the two formers are corresponding to the 4f65d1-4f7 transition of Eu2+, the latter is originated from the 5D0-7FJ (J=1,2,3,4) transitions of Eu3+. The investigated results indicate that part of Eu3+ can be self-reduced to Eu2+ in the matrix and will reach the maximum when x=0.1 mol. When co-doping Ce3+ ions, the luminescent colors of the phosphors Ba1.97-yZn0.9 Mg0.1Si2O7:0.03Eu,yCe3+ can be tunable from green to white to orange area. It had been found that the nominal composition Ba1.96Zn0.9Mg0.1Si2O7:0.03Eu,0.01Ce3+ phosphor provides a white emission (0.323, 0.311) that is very close to the standard white (x=0.33, y=0.33), which shows that it is a potential white phosphor for LED-based UV-chip. The energy transfer processes among rare earths and the luminescent mechanism were discussed.
Keywords:Ba2Zn1-xMgxSi2O7  Ba1.97-yZn0.9Mg0.1Si2O7:0.03Eu,yCe3+    self-reduction  white-light phosphor
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